Treatment of textile materials



United States Patent TREATMENT OF TEXTILE MATERIALS Fred E. Condo, El Cerrito, and Carl W. Schroeder,

Orinda, Calif, assignors to Shell Development Company, New York, N.Y., a corporation-of Delaware No Drawing. Application April 27, 1956 Serial No. 580,993

11 Claims. (Cl. 117-139.4)

This invention relates to the treatment of textile materials. More particularly, the invention relates to a method for preparing textile materials that have improved crease and shrink resistance and no chlorine retention.

Specifically, the invention provides a new process for preparing crease resistant and shrink resistant, textile ma terials having no chlorine retention and improved washability comprises impregnating the textile material with an aqueous medium containing a polyepoxide which has at least one epoxy group in an internal position, i.e., has at least one group, and certain amounts of an epoxy curing agent and then heating to effect cure. The invention further provides improved fabrics prepared by the afore-describe'd process.

This application is a continuation-in-part of our application Ser. No. 259,504, filed December 1, 1951, now US. Patent No. 2,752,269.

Many of the textile fabrics, such as cotton and rayon, have rather poor resilience, i.e., they are easily creased or wrinkled when crushed or otherwise subjected to localized physical force. In addition, many of these fabrics have poor dimensional stability as exemplified by poor resistance to shrinkage. In order to overcome these shortcomings it has been common practice to treat the fabric with a resin, such as a ureaor melamineformaldehyde resin that could be subsequently insolubilized within the fabric fibers. While this method has met with some success with colored fabrics, it has been of little or no use in the treatment of white goods that may be subjected to bleaching. It has been found that during the bleaching process, the added resins retain considerable quantities of the chlorine and when the fabric is subsequently exposed to heat as in ironing or hot-air drying, the cloth is charred or discolored and the strength of the material seriously degraded. In addition, many of the fabrics treated with these resins have poor washability, i.e., the resin is easily lost from the fabric after a few washings with soap and water.

It is an object of the invention, therefore, to provide a new method for treating textile materials. It is a further object to provide a process for rendering textile materials crease .and shrink resistant without giving a harsh feel and undue stiffness to the material. It is a further object to provide a method for making textile materials more resilient. It is a further object to provide a method for preparing crease and shrink-resistant textile materials that have no chlorine retention. It is a further object to provide a'method where the crease and shrink resistant properties will be resistant to washing. It is a further object to provide a method for treating textile materials which, while imparting wrinkle and shrink resistance to the fabrics, has. little if any detrimental elfect on the other desired properties of the fabric.

2,886,472 Patented May 12, 1959 ICC? It is still a further object to provide textile materials having many improved properties. Other objects and advantages of the invention will be apparent from the following detailed description thereof.

It has now been discovered that these and other objects may beaccomplished by the novel process of the invention which comprises impregnating the textile material with an aqueous medium containing a polyepoxide which has at least one epoxy group in an internal position, i.e., has at least one a group, and certain amounts of an epoxy curing agent and then heating to etfect cure. The fabrics treated in this manner, even with relatively small amounts of the polyepoxide, have excellent resistance to creasing and rubbing and still have a soft feel. The fabrics also have improved resistance to shrinkage and are quite resilient.

It'has further been surprisingly found that the fabrics treated in the above-described manner have no ability to retainchlor'ine and the coated fabrics may be bleached or otherwise exposed to chlorine without danger of being discolored, charred or weakened during subsequent heat treatments. In addition, the fabrics have been found to have improved washability and can be washed numeroustimes without danger of losing any substantial amount of the polyepoxide resin.

The material to be used in the process of the invention includes those having at least one internal epoxy group, i.e., at least one group, and at least one other epoxy group which may be a terminal epoxy group, i.e., may be a Hie-ch orogroup, or an internal epoxy group. These groups may be in an open or closed chain portion of the molecule. The polyepoxide is preferably aliphatic and free of elements other than carbon, hydrogen, oxygen and chlorine.

Examples of these polyepoxides include the epoxysubstituted hydrocarbons, such as, for example, vinyl cyclohexene dioxide, 2,3,5,6-diepoxyoctane, 2,3,6,7-diepoxydodecane, 1,2-epoxy-3-(2,3-epoxypropyl)cyclohexane, 2,2-bis(epoxycyclohexyl)propane, and 1,2-epoxy-4- (3,4-epoxybutyl)cyclohexane.

Another group of these polyepoxides include the ethers of epoxy-substituted cycloalkanol alcohols such as epoxycyclohexanol. Examples of the group include, among others, di(epoxycyclohexyl) ether, di(epoxycyclopentyl)- ether, glycidyl ether. of t2,3-epoxycyclohexanol, epoxybutyl ether of 2,3-epoxycyclohexanol and epoxyhexyl ether of 3,4-epoxycyclohexanol.

Other examplesinclude the epoxidized esters of the polyethylenically unsaturated monocarboxylic acids, such as epoxidized linseed, soyabean, perilla, oiticia, tung, walnut and dehydrated castor oil, methyl linoleate, butyl linoleate, ethyl 9,12-octadecadienoate, butyl 9,12,15-octadecatrienoate, ethyl elaeostearate, octyl 9,12-octadecadienoate, methyl elaeostearate, monoglycerides of tung oil fatty acids,-monoglycerides of soyabean oil, sunflower, rapeseed, hempseed, sardine, cottonseed oil, and the like.

Another group of the epoxy-containing materials used in the process of the invention include the epoxidized. esters of unsaturated monohydric alcohols and polycarboxylic acids, such as, f or example, di(2,3-epoxybutyl) adipate, di(2,3-epoxybutyl) oxalate, di(2,3-epoxyhexyl) succinate, di(3,4-epoxybutyi)' maleate, di(2,3-epoxyoctyl) pimelate, di(2,3-epoxybutyl) phthalate, di(2,3-epoxyoctyl) tetrahydrophthalate, di(4,5-epoxydodecyl) maleate, di(2,3-epoxy-butyl) terephthalate, di(2,3-epoxypentyl) thiodipropionate, di(5-,6'- epoxytetradecyl) diphenyldicarboxylate, di(3,4-epoxyheptyl) sulfonyl-dibutyrate, tri(2,3-epoxybutyl) 1,2,4-butanetricarboxylate, di(5,6 epoxypentadecyl) tartarate, di(4,5 epoxytetradecyl) maleate, di(2,3-epoxybutyl) azelate, di(2,3-epoxybutyl) citrate, di(5,6-epoxyoctyl) cyclohexane-l,3-dicarboxylate, di(4,5-epoxyoctadecyl) malonate.

Another group of the epoxy-containing materials include those epoxidized esters of unsaturated alcohols and unsaturated carboxylic acids, such as 2,3-epoxycyclohexyl epoxypropionate, 2,3-epoxybutyl 3,4-epoxypentanoate, 3,4-epoxyhexyl 3,4-epoxypentanoate, 3,4-epoxycyclohexyl 3,4-cyclohexanoate, 3,4epoxycyclohexy1 4,5- epoxyoctanoate, and the like.

Still another group of the epoxy-containing materials include epoxidized derivatives of polyethylenically unsaturated polycarboxylic acids, such as, for example, dimethyl 8,9,12,13-diepoxyeicosanedioate, dibutyl 7,8,11, lZ-diepoxyoctadecanedioate, dioctyl l0,11-diethyl-8,9,12, l3-diepoxyeicosanedioate, dihexyl 6,7,10,11-diepoxyhexa-- decanedioate, didecyl 9-epoxyethyl-10,ll-epoxyoctadecenedioate, dibutyl 3-butyl-3,4,5,6-diepoxycyclohexane-1, 2-dicarboxylate, dicyclohexyl 3 ,4,5 ,6-diepoxycyclohexane- 1,2-dicarboxylate, dibenzyl 1,2,4,S-diepoxycyclohexane- 1,2-dicarboxylate and diethyl 5,6-10,1l-diepoxyoctadecyl succinate.

Still another group comprises the epoxidized polyesters obtainedby reacting an unsaturated polyhydric alcohol and/or unsaturated polycarboxylic acid or anhydride groups, such as, for example, the polyester obtained by reacting 8,9,12,13-eicosadienedioic acid with ethylene gly col, the polyester obtained by reacting diethylene glycol with 2-cyclohexene-1,4-dicarboxylic acid and the like, and mixtures thereof.

Particularly preferred materials to be used according to the process of the invention comprise the epoxy-substituted hydrocarbons, and ethers of epoxy alcohols and epoxy-substituted cyclohexanols, the epoxidized esters of polyethylenically unsaturated monocarboxylic acids containing not more than 22 carbon atoms, the epoxidized esters of polyethylenically unsaturated polycarboxylic acids containing not more than 25 carbon atoms, and the epoxidized esters of ethylenicaly unsaturated monohydric alcohols and ethylenically unsaturated carboxylic acids containing not more than 22 carbon atoms.

Especially preferred are those materials having one or more internal epoxy groups and one or more terminal epoxy groups, such as vinyl cyclohexene dioxide, glycidyl ether of epoxy cyclohexanol, epoxidized acrylic acid ester of cyclohexanol and glycidyl ester of epoxycyclohexanecarboxylic acid. Many of the above-described epoxy-containing materials are preferably obtained by epoxidizing the corresponding unsaturated compounds. Thus, the compounds, such as dimethyl 8,9,12,l3-diepoxyeicosanedioate may be obtained by epoxidizing dimethyl 8,9,12,l3-eicosadienedioate. The epoxidation may be accomplished by reacting the unsaturated compound with an epoxidizing agent. Organic peracids, such as performic, peracetic, perbenzoic acid and the like are preferred agents for this reaction.

The amount of the epoxidizing agent employed will vary over a considerablerange depending upon the type of product desired. In general, one should employ at least one mole of the oxidizing agent, such as perbenzoic acid, for every ethylenic group to be epoxidized. Thus to produce epoxidized dicrotyl adipate from dicrotyl adipate, one should react the unsaturated ester with at least two moles of perbenzoic acid. In some cases, it is rather difi'icult to effect epoxidation of all of the ethylenic groups and if a completely epoxidized product is required,

additional epoxidizing agent and/or longer reaction period may be required.

The temperature employed during the epoxidation may vary over a considerable range depending upon the type of reactants and epoxidizing agents selected. It is generally desirable to maintain the temperature between -20 C. to 100 C. Preferred temperatures range from about 10 C. to room temperature, e.g., about 20 C. Atmospheric, superatmospheric, or subatmospheric pressures may be employed as desired.

The epoxidized product obtained by this method may be recovered from the reaction mixture by any convenient means known to the art, such as distillation, extraction, fractional precipitation and the like.

The polyepoxides described above are applied to the textile material in the form of an aqueous medium. If the polyepoxides are water-soluble they may be used directly as a water solution. Otherwise, it may be desirable to employ solvents,-emulsifying agents and the like in the aqueous medium in order to obtain the proper concentration of the polyepoxide. Examples of solvents that may be used in the water solutions include, among others, ethyl alcohol, isopropyl alcohol, methanol, and the like. Particularly preferred mediums of this type comprise water-alcohol mixtures having a weight ratio varying from 3 :1 to 1:5. Emulsifying agents employed for this purpose are preferably those that are free of nitrogen and strong acidic groups, such as the monooleate of sorbitan polyoxyethylene, the trioleate of sorbitan polyoxyethylene, sorbitan tristearate, sorbitan monolaurate, polyoxyethylene ethers of alkylphenols, carboxymethylcellulose, starch, gum arabic, aryl and alkylated aryl sulfonates, such as cetyl sulfonate, oleyl sulfonate, sulfonated mineral oils, and the like, and mixtures thereof. The emulsifying agents are generally employed in amounts varying from 0.1% to 10% by weight and more preferably from 1% to 5% by weight.

The amount of the polyepoxide in the impregnating solution may vary over a considerable range depending chiefly on the amount of resin to be deposited on the fabric and this in turn will depend on the number of applications and the pick-up allowed per application. When the solution is applied but once, with a to pick-up by weight of the fabric in the dry state, a concentration ranging from 3% to 25% by weight will ordinarily suffice. If less than 80% pick-up is permitted, the concentration may in some cases go as high as 30% to 50%.

The hardening or curing agents may be added to the polyepoxide solution before it is applied to the fabric or it may be applied by spraying or other suitable methods to the fabric after it has been impregnated with the poly- .epoxide. The curing agents are preferably added to the solution before it is applied to the fabric. Preferred curing agents to be used include the acid and acid-acting curing agents, such as the organic and inorganic acids and anhydrides as citric acid, acetic acid, acetic acid anhydride, butyric acid, caproic acid, phthalic acid, phthalic acid anhydride, tartaric acid, aconitic acid, oxalic acid, succinic acid, succinic acid anhydride, lactic acid, maleic acid, maleic acid anhydride, fumaric acid, glutaconic acid, 1,2,4-butanetricarboxylic acid, isophthalic acid, terephthalic acid, malonic acid, 1,1,5-pentanetricarboxylic acid, acetoacetic acid, naphthalic acid, trimallitic acid, phosphoric acid, boric acid, sulfonic acid, phosphinic acid, perchloric acid, persulfuric acid, p-toluenesulfonic acid, ethanesulfonic acid, and the like compounds having at least one sulfonic group linked to a hydrocarbon radical. The borontrifluoride complexes, such as the p-cresol and urea complex, may also be used as curing agents. Amines may be used but are less preferred.

Particularly preferred curing agents comprise the metal salts and preferably salts of metals having an atomic weight between 24 and 210, and preferably in groups I r to IV'and VIII of the periodic table of ele me'nts and inorganic acids the anion portion of which contains at least two dissimilar elementshaving an atomic weight above 2, and particularly inorganic acids of the formula wherein X is a non-metal having an atomic weight above 2, Z is an element which gains from 1 to 2 electrons in its outer orbit, such as oxygen and fluorine, w is an integer, y is an integer greater than 1 and a equals the valency of the radical (X) (Z),,, such as sulfuric acid, fluoboric acid, fluosilicic acid, persulfuric acid, phosphoric acid and the like. Examples of these preferred agents include, among others, zinc fluoborate, zinc sulfate, magnesium fluoborate, magnesium perchlorate, potassium persulfate, copper fluoborate, copper persulfate, cobaltic fluoborate, chromic nitrate, magnesium nitrate, calcium phosphite, and the like.

Coming under special consideration'as curing agents are the above-described organic polycarboxylic acids, boron-trifluoride complexes and the above-described metal salts.

The above-described curing agents are to be used in sufficient amount to convert the polyepoxide to the desired insoluble infusible state. The epoxy groups in the internal position are less reactive to the curing agents under the conditions of the present process than those in the terminal position so the amount of curing agent used must be greater, such as 1.5 times greater, than that used when the compounds have all terminal epoxy groups as the polyglycidyl ethers. The organic acids are used .in amounts of from 2% to with the polyglycidyl ethers so in the present invention they are preferably used in amounts varying from about 3% to by weight of polyepoxide. The boron-trifluoride complexes are used inamounts from 1.0% to 7.5% with the polyglycidyl ethers so in the present invention they are preferably used in amounts varying from 1.5% to 10% by weight of polyepoxide. The metal salts are employed in amounts varying from 0.5% to 40% with the polyglycidyl ethers so in the present invention they are preferably used in amounts varying from 0.75% to 60% by weight of the polyepoxide.

The solutions employed to treat the textiles may also contain plasticizers to improve their flexibility, though these should not be present in such proportions as to render the finished materials soft or sticky at temperatures and humidities to which they would be exposed. It is found, however, that the substances employed in the present invention yield products which are sufficiently flexible for most purposes without the use of plasticizers.

- Among plasticizers that may be used according to the present invention may be mentioned organic and inorganic derivatives of phenols, for example, diphenylol propane and triphenyl and tricresyl phosphates, alkyl phthalates, for example, diethyl phthalate and glycol phthalates, diethyl tartrate, derivatives of polyhydric alcohols, for example, mono-, diand triacetin, and products obtained by condensing polyhydric alcohols with themselves or with aldehydes or ketones. The compositions may also contain natural resins, e.g., shellac, rosin, and other natural resins and synthetic or semi-synthetic resins, e.g., ester gum, polyhydroxypolybasic alkyd resins, phenolaldehyde and urea-aldehyde resins.

Textile softening agents, and particularly those of the cationic-type as stearamidoethyl diethyl methyl quaternary ammonium methyl sulphate, trimethyl ammon um methyl sulphate of monostearylmetaphenylenedramme, s-di(1,2-palmitamidoethyl) urea monoacetate, palmityl amine hydrochloride, and the like, and mixtures thereof, may also be added in varying amounts to improve the feel of the treated fabrics.

The application of the solution containing the polyepoxide to the textile fabric may be effected in any suitable manner, the method selected depending upon the results desired. If it is desired to apply the solution only to one surface of the material, as, for example, when ;it is desired to treat the back only'of a fabric having-a face of artificial or natural silk and a cotton back, the application may be etfected by spraying or by means of rollers, or the composition may be spread upon the surface by means of a doctor blade. When, however, it is desired to coat both surfaces of the material, or if the material is to be thoroughly impregnated with it, the fabrics may be simply dipped in the solution or run through conventional-type padding rollers. The solutions may also be applied locally to the material, for example, by means of printing rollers or by stencilling.

The amount of the polyepoxides to be deposited on the fabric will vary over a wide range depending upon the degree of wrinkle-resistance and shrink-resistance desired in the finished material. If the fabric is to have a soft feel, such as that intended for use for dresses, shirts, etc., the amount of polyepoxide deposited will generally vary from 3% to'20% by weight of the fabric. If stiffer materials are required such as for shoe fabrics, draperies, etc. still higher amounts of resins, such as of the order of 25% to 50% by weight may be deposited. In determining the amount of resin deposited, it should, of course, be remembered that the presence of the polyepoxides in a few instances causes a slight decrease in tear strength of the fabric and the amount deposited should be balanced between the desired wrinkle resistance and the desired tear strength.

If the desired amount of polyepoxide deposited in the fabric is not obtained in one application, the aqueous medium may be applied again 'or as many times as desired to bring the amount of the polyepoxide resin up to the desired level. p v 7 After the textile material has been impregnated with the aqueous medium containing the polyepoxide, the treated material is then dried for a short period. This is generally accomplished by exposing the wet sheets to hot gas at temperatures ranging from 50 C. to C. The period of drying will depend largely on the amount of pick-up permitted during the application of thesolution, and the concentration of the polyepoxide. In most instances, drying periods of from 5 to 30 minutes should be suflicient.

The dried fabric is then exposed to relatively high temperatures to accelerate the cure of the polyepoxides. Temperatures used for this purpose generally range from C. to 200 C., and more preferably from 100 C. to C. ,At these preferred temperatures, the cure can usually be accomplished in from 3 to 10 minutes. Exposures of less than 3 minutes, e.g., 1 minute, may probably be used in continuous, commercial processing.

The process of the invention may be applied to the treatment of any textile material. Such materials include those prepared from the natural or artificial textile materials, e.g., cotton, linen, silk, rayon (regenerated cellulose), jute, hemp, animal fibers, such as wool, hair, mohair, nylon, Dacron and terylene mixtures thereof. While the invention has been particularly described with relation to the treatment of Woven fabrics, it may also be applied to other materials, for example, knitted or netted materials. 7

The materials treated according to the process of the invention will have excellent crease and shrink resistance as well as good resiliency and flexibility and may be used for a wide variety of important applications. The woven cotton, rayon and wool fabrics, both colored and white, containing conventional amounts of resin, e.g., 25 to 50% may be used in other applications demanding more crispness and fullness such as the preparation of rugs, carpets, plushes, drapes, upholsteries, shoefabrics, and the like.

To illustrate the manner in which the invention may be carried out, the following examples are given. It is to be understood, however, that the examples are for the purpose of illustration and the invention is not to be impregnated cloth was-then dried at 60 Example I This example illustrates the use of vinyl cyclohexene dioxide in the treatment of cotton.

100 parts of vinyl cyclohexene dioxide was added to water to form a 9% solution. 10 parts of anhydrous zinc fluoborate was added to the solution with stirring and the resulting mixture padded on cotton fabric by.

. means of a ButterWorth-B-Roll laboratory padder. The

cloth'after padding showed a 65% wet pick-up. The

C. for minutes'and cured at 160 C.'for 5 minutes. The finished product waswashed and rinsed three times in warm water to remove any soluble material.

. The cloth treated in the above-described manner had excellent crease and shrink resistance, no chlorine .reten tion, a soft-feel, good color and excellent washability. The cloth had a crease recovery value of 111. For comparison, cloth treated with aqueous solution of a polyglycidyl ether using 5 parts of curing agent had a crease recovery of 108.

Example II This example illustrates the use of 2,2-bis(2,3-epoxycyclohexyl) propane in the treatment of cotton fabric.

100 parts of 2,2-bis(2,3-epoxycyclohexyl) propane was added to water and then 50 parts of a 10% aqueous solution of 85% hydrolyzed polyvinyl acetate added with stirring. The mixture was then diluted with water to form a 10% solution of the polyepoxide.

10 parts of zinc fluoborate was then added to the solution with stirring and the resulting mixture padded on cotton fabric by means of a Butterworth-3-Roll laboratory padder. The cloth after padding showed a 65% wet pick-up. The impregnated cloth was then dried at 60 C. for 5 minutes and cured at 160 C. for 5 minutes. The finished product was washed and rinsed three times in warm water to remove any soluble material.

The cloth treated in the above-described manner had good crease and shrink resistance, no chlorine retention, a soft feel, good colorand good washability.

Ex'ample III This example illustrates the use of epoxidized tetrahydrobenzyl tetrahydrobenzoate in the treatment of cotton fabric.

100 parts of epoxidized tetrahydrobenzyl tetrahydrobenzoate was added to water and then 50 parts of a 10% aqueous solution of hydrolyzed polyvinyl acetate was added with stirring. The mixture was then diluted with water to form a 12% aqueous solution of the polyepoxide.

10 parts of magnesium perchlorate was added to the solution with stirring and the resulting mixture padded on cotton fabric by means of a Butterworth-3-Roll laboratory padder. The cloth after padding showed a 65% wet pick-up. The impregnated cloth was then dried at 60 C. for 5 minutes and cured at 160 C. for 5 minutes. The finished product was washed and rinsed three times in warm water to remove any soluble material.

The cloth treated in the above-described manner had excellent crease and shrink resistance, no chlorine retention, a soft feel, good color and excellent washability.

Related results are obtained by replacing the epoxidized tetrahydrobenzyl tetrahydrobenzoate in the above process with equivalent amounts of each of the following: epoxidized 'cyclohexenyl' tetrahydrobenzoate, epoxidized cyclohexenyl aerylate and epoxidized cyclohexenyl octenoate.

Example IV This example illustrates the use of epoxidized dimethyl 8,9,11,12-eicosadienedioate in the treatment of cotton fabric. One hundred parts of epoxidized dimethyl 8,9,11,12-eicosadienedioate was mixed with water and then 50 parts of a 10% aqueous solution of hydrolyzed polyvinyl acetate was added with stirring. The mixture was then diluted with water to form a 12% aqueous solution of the polyepoxide.

10 parts of zinc fiuoborate was added to the solution with stirring and the resulting mixture padded on cotton fabric by means of a Butterworth-3-Roll laboratory padder. The cloth after padding showed a wet pick-up. The impregnated cloth was then dried at 60 C. for 5 minutes and cured at 160C. for 5 minutes. The finished product was washed and rinsed three times in warm water to remove any soluble material.

The cloth treated in the above-described manner had excellent crease and shrink resistance, no chlorine retention, a soft feel, good color and excellent washability.

Example V This example illustrates the use of vinyl cyclohexene dioxide in the treatment of rayon.

100 parts of vinyl cyclohexene dioxide was added to water to form a 9% solution. 10 parts of magnesium perchlorate was then added with stirring and the resulting mixture padded on rayon cloth by means of a Butterworth-3-Roll laboratory padder. The cloth was then dried at 60 C. for 5 minutes and cured at 160 C. for 5 minutes. The finished product was washed and rinsed three times in warm water to remove any soluble material.

The cloth treated in the above-noted manner had good crease and shrink resistance, soft feel, good color, no chlorine retention and improved washability.

Example VI This example illustrates the use of epoxidized dicrotyl phthalate in the treatment of cotton fabric.

100 parts of epoxidized dicrotyl phthalate was mixed with water and then 50 parts of a 10% aqueous solution of hydrolyzed polyvinyl acetate was added with stirring. The mixture was then diluted with water to form a 10% aqueous solution of the polyepoxide.

10 parts of zinc fiuoborate was added to the solution with stirring and the resulting mixture padded on cotton fabric by means of a Butterworth-3-Roll laboratory padder. The cloth after padding showed a 65 wet pick-up. The impregnated cloth was then dried at 60 C. for 5 minutes and cured at 160 C. for 5 minutes. The finished product was washed and rinsed three times in warm water to remove any soluble material.

The cloth treated in the above-described manner had excellent crease and shrink resistance, no chlorine retention, a soft feel, good color and good washability.

Related results are obtained by replacing the epoxidized dicrotyl phthalate in the above process with equivalent amounts of each of the following: epoxidized dicrotyl adipate, epoxidized di(3-pentenyl) terephthalate and epoxidized dicrotyl succinate.

Example VII This example illustrates the use of the glycidyl ether of 2,3-epoxycyclohexanol in the treatment of cotton.

stirring and the resulting mixture padded on cotton fabric by means of a Butterworth-3-Roll laboratory padder. The cloth after padding showed a 65% wet pick-up.

. The impregnated cloth was then dried at 60 C. for 5 minutes and cured at C. The finished product was then washed and rinsed. The cloth treated in this manner had good crease and shrink resistance, no chlorine retention, a soft feel, good color and excellent washability.

We claim as our invention:

1. A process for treating textile materials made up substantially of cellulosic material to make them creaseresistant and shrink resistant without affecting feel and chlorine-retentive properties which comprises impregnating the textile material with an aqueous medium containing a polyepoxide having at least one group, and from 1.5% to by weight of the polyepoxide of a borontrifiuoride complex, and then heating the treated fabric to cure the polyepoxide.

2. A process for treating cellulosic textile materials made up substantially of cellulosic material to make them crease and shrink resistant which comprises impregnating the textile material with an aqueous medium containing a polyepoxide having at least one group, and from 0.75% to 60% by weight of the polyepoxide of a metal salt of a metal having an atomic weight between 24 and 210 and an inorganic acid, and then heating the treated material to cure the polyepoxide.

3. A process as in claim 2 wherein the polyepoxide is vinyl cyclohexene dioxide.

4. A process as in claim 2 wherein the polyepoxide is bis(epoxycyclohexyl)propane.

5. A process as in claim 2 wherein the polyepoxide is epoxidized tetrahydrobenzyl tetrahydrobenzoate.

10 6. A process as in claim 2 wherein the textile material is cotton.

7. A process as in claim 2 wherein the textile material is rayon.

8. A process for treating textile material made up substantially of cellulosic material to make the material crease and shrink resistant which comprises impregnating the textile material with an aqueous medium containing a polyepoxide having at least one 0 -o-o -oogroup, and from 3% to 15% by weight of the polyepoxide of an organic polycarboxylic acid, and then heating the treated material at a temperature between C. and 200 C. for a short period to effect cure of the polyepoxide.

9. A process as in claim 8 wherein the polyepoxide is vinyl cyclohexene dioxide.

10. A process as in claim 8 wherein the polyepoxide is an epoxidized polyethylenically unsaturated carboxylic acid ester.

11. A process as in claim 8 wherein the textile material is cotton.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A PROCESS FOR TREATING TEXTILE MATERIALS MADE UP SUBSTANTIALLY OF CELLULOSIC MATERIAL TO MAKE THEN CREASERESISTANT AND SHRINK RESISTAN WITHOUT AFFECTING FEEL AND CHLORINE-RETENTIVE PROPERTIES WHICH COMPRISES IMPREGNATING THE TEXTILE MATERIAL WITH AN AQUEOUS MEDIUM CONTAINING A POLYEPOXIDE HAVING AT LEAST ONE. 